JPH061354B1 - Silver halide photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material having a hydrophilic colloid layer colored with a novel dye.

BACKGROUND ART In a silver halide photographic light-sensitive material, a photographic emulsion layer and other hydrophilic colloid layers are often colored for the purpose of absorbing light in a specific wavelength range.

When it is necessary to control the spectral composition of light to be incident on the photographic emulsion layer, a coloring layer is usually provided on the side farther from the support than the photographic emulsion layer. Such a colored layer is called a filter layer. When there are multiple photographic emulsion layers, the filter layer may be located between them.

An image based on the fact that the light scattered during or after passing through the photographic emulsion layer is reflected on the interface between the emulsion layer and the support or on the surface of the light-sensitive material on the side opposite to the emulsion layer and re-enters the photographic emulsion layer. For the purpose of preventing the blurring, i.e., halation, a coloring layer called an antihalation layer is provided between the photographic emulsion layer and the support or on the surface of the support opposite to the photographic emulsion layer. When there are a plurality of photographic emulsion layers, an antihalation layer may be placed between the layers.

Decrease in image sharpness due to light scattering in photographic emulsion layer (This phenomenon is generally called irradiation)
Coloring of the photographic emulsion layer is also carried out in order to prevent this.

These hydrophilic colloid layers to be colored usually contain a dye. This dye needs to satisfy the following conditions.

(1) It has a proper spectral absorption according to the purpose of use.

(2) Photochemically inactive. That is, it should not adversely affect the performance of the silver halide photographic emulsion layer in a chemical sense, such as reduction in sensitivity, latent image regression, or fog.

(3) It should not be decolorized in the course of photographic processing or be dissolved in a processing solution or washing water to leave no harmful coloring on the photographic light-sensitive material after processing.

(4) Do not diffuse from the dyed layer to other layers.

(5) It has excellent stability over time in a solution or photographic material and should not discolor or fade.

In particular, regarding (4) above, when the colored layer is a filter layer or an antihalation layer placed on the same side of the support as the photographic emulsion layer, those layers are selectively colored. However, it is often necessary to prevent the other layers from being colored substantially. This is because otherwise, not only the detrimental spectroscopic effect is exerted on other layers, but also the effect as a filter layer or an antihalation layer is diminished. Thus, wet contact between the dyed layer and other hydrophilic colloidal layers often results in the diffusion of some of the dye from the former to the latter. The diffusion of such a dye largely depends on the chemical structure of the dye used.

Many efforts have been made to find dyes satisfying these conditions. For example, British Patent No. 506,3
85, US Pat. Nos. 3,247,127 and 2,53.
3,472, 3,379,533, oxonol dyes as described in British Patent No. 1,278,621, hemioxonol dyes represented by dyes described in British Patent No. 584609, US Pat. No. 2,29
Styryl dyes represented by the dyes described in US Pat. No. 8,733, merocyanine dyes such as the dyes described in US Pat. No. 2,493,747, US Pat. No. 2,843,48.
Cyanine dyes represented by the dyes described in No. 6 are mentioned.

Most of the dyes that are decolorized during the processing of photographic emulsions are sulfites (or acidic sulfites) contained in the developing solution.
Alternatively, they are decolorized by alkaline conditions with them. For example, as described in US Pat. No. 506,385.

Also, U.S. Pat. Nos. 3,002,837 and 3,389,
In 994, a bis type dye having a pyrazolone ring structure is started.

However, each of the dyes described in the conventional literature has merits and demerits, and when used in a silver halide photographic light-sensitive material, it cannot be said that they satisfy all the above conditions (1) to (5). There is a demand for the development of high-performance dyes that can be used in silver halide photographic light-sensitive materials.

DISCLOSURE OF THE INVENTION The first object of the present invention is to obtain a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a novel dye which selectively dyes a specific layer and does not diffuse to other layers. Is.

The second object of the present invention is to provide a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a novel dye which is decolorized in the photographic processing and does not adversely affect the photographic characteristics of the photographic emulsion, particularly the spectral sensitization. Is to get.

It has been found that the above objects can be achieved by a silver halide photographic light-sensitive material containing at least one compound represented by the following general formulas (I) to (VI).

That is, the present invention provides a silver halide photographic light-sensitive material containing at least one compound represented by the following general formulas (I) to (VI).

General formula (I) General formula (II) General formula (III) General formula (IV) General formula (V) General formula (VI) (In the formula, X ₁ , X ₂ , X ₃ and X ₄ may be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, a carboxy group, a substituted amino group, a carbamoyl group or a sulfamoyl group. Represents a group or an alkoxycarbonyl group.

R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and each represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, an acyl group, Represents a sulfonyl group. General formula (II
In I) to (VI), R ₁ , R ₂ or R ₃ , R ₄ may form a 5- or 6-membered ring.

Z ₁ , Z ₂ , Z ₃ and Z ₄ may be the same or different and represent an electron-withdrawing group. Also Z ₁ and Z ₂ or Z ₃
And Z ₄ may be linked to each other to form a ring. Z ₅ , Z
₆ may be the same or different and represent an atomic group forming a ring, and Z ₇ and Z ₈ may be the same or different and represent an electron-withdrawing group.

Y ₁ and Y ₂ represent a divalent linking group, and Y ₃ and Y ₄ may be the same or different and represent a divalent linking group having an electron-withdrawing property.

L represents an unsubstituted or substituted methine group. m and n are 0
Or 1. ) The dye compounds represented by the general formulas (I) to (VI) will be described in more detail.

In the formula, X ₁ , X ₂ , X ₃ and X ₄ may be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having preferably 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. Alkoxy group, hydroxy group, carboxyl group, substituted amino group (amino group substituted by an acyl group derived from an aliphatic carboxylic acid or sulfonic acid having 1 to 6 carbon atoms, preferably 1 to 6 carbon atoms) An alkylamino group, a dialkylamino group having 1 to 6 carbon atoms, etc.), a carbamoyl group having 2 to 7 carbon atoms, or a sulfamoyl group having 1 to 6 carbon atoms,
Alternatively, it represents an alkoxycarbonyl group having preferably 2 to 6 carbon atoms.

R ₁ , R ₂ , R ₃ , and R ₄ may be the same or different from each other, and are a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms (the substituent is a halogen atom, a hydroxy group, a cyano group). Group, alkoxy group, acyl group, acyloxy group, acylamino group, carbomoyl group, alkylamino group, dialkylamino group, carboxyl group, alkoxycarbonyl group, sulfonyl group, sulfonylamino group, sulfamoyl group, sulfo group, aryl group, etc.),
An alkenyl group having preferably 2 to 6 carbon atoms, an unsubstituted or substituted aryl group (preferably an unsubstituted or substituted phenyl group (as a substituent, a halogen atom, a cyano group, a sulfo group, a hydroxy group, a carboxyl group, an alkoxy group ,
Alkyl group, nitro group, etc.)}, preferably having 2 carbon atoms
To an acyl group, preferably an alkylsulfonyl group having 1 to 6 carbon atoms, or an unsubstituted or substituted arylsulfonyl group (preferably an unsubstituted or substituted phenyl group (as a substituent, a halogen atom, a cyano group, a sulfo group , Hydroxy group, alkoxy group, alkyl group, etc.)}.

Z ₁ , Z ₂ , Z ₃ , and Z ₄ may be the same or different, and preferably have an acyl group having 2 to 13 carbon atoms, a carbamoyl group having 2 to 13 carbon atoms, a carboxy group, and a carbon number. Is preferably 2 to 10 unsubstituted or substituted alkoxycarbonyl group (as a substituent, a halogen atom, a hydroxy group, a cyano group, an alkoxy group, an acyl group, an acylamino group, an alkylamino group, a dialkylamino group, a carboxy group, an alkoxy group). Carbonyl group, sulfonyl group, sulfonylamino group, sulfo group, aryl group, etc.), unsubstituted or substituted aryloxycarbonyl group (the substituent is a halogen atom, an alkyl group, an alkoxy group, a nitro group, a hydroxy group, a carboxy group, Sulfo group, cyano group, unsubstituted or substituted amino group (substituent is an alkyl group, An acyl group, an alkylsulfonyl group, etc.), an alkoxycarbonyl group, etc.}, preferably a sulfonyl group having 1 to 12 carbon atoms, and preferably 1 to 12 carbon atoms.
12 represents an electron-withdrawing group such as a sulfamoyl group or a cyano group. In addition, Z ₁ and Z ₂ are linked to form a ring (for example,
(Pyrazolone ring, pyrazolotriazole ring, pyrazoloimidazole ring, oxindole ring, oxyimidazopyridine ring, isoxazolone ring, barbituric acid ring, dioxytetrahydropyridine ring, indandione ring, etc.)
May be formed. The same applies to Z ₃ and Z ₄ .

Z ₅ and Z ₆ may be the same or different and each have a ring (for example, a pyrazolone ring, a pyrazolotriazole ring, a pyrazoloimidazole ring, an oxindole ring, an oxyimidazopyridine ring, an isoxazolone ring, a barbituric acid ring,
Dioxytetrahydropyridine ring, indandione ring, etc.). Z ₇ and Z ₈ may be the same or different and preferably have 2 to 13 carbon atoms.
An acyl group, a carbomoyl group having preferably 2 to 13 carbon atoms, a carboxy group, an unsubstituted or substituted alkoxycarbonyl group having preferably 2 to 10 carbon atoms (as a substituent, a halogen atom, a hydroxy group, a cyano group, Alkoxy group, acyl group, acylamino group, alkylamino group,
Dialkylamino group, carboxy group, alkoxycarbonyl group, sulfonyl group, sulfonylamino group, sulfo group, aryl group, etc.), unsubstituted or substituted aryloxycarbonyl group (substituent is a halogen atom, alkyl group, alkoxy group, nitro Group, hydroxy group, carboxy group, cyano group, unsubstituted or substituted amino group (substituent is alkyl group, acyl group, alkylsulfonyl group, etc.), alkoxycarbonyl group, etc.}, preferably having 1 to 12 carbon atoms. It represents an electron-withdrawing group such as a sulfonyl group, a sulfamoyl group having preferably 1 to 12 carbon atoms, and a cyano group.

More specifically, in the formula, X ₁ , X ₂ , X ₃ ,
X _{4 s} may be the same or different and each is a hydrogen atom, a halogen atom (eg, chloro atom, bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms (eg, methyl, ethyl, propyl, hexyl, etc.), 1 to 1 carbon atoms. 6-alkoxy group (eg, methoxy, ethoxy, butoxy, hexyloxy, etc.), hydroxy group, carboxy group, amino group substituted with an acyl group derived from an aliphatic carboxylic acid having 1 to 6 carbon atoms or sulfonic acid (eg, Acetylamino, hexylcarbonylamino, methanesulfonylamino, ethanesulfonylamino, hexanesulfonylamino, 3
-Sulfopropylcarbonylamino, etc.), carbon number 1 to
6 alkylamino groups (eg, methylamino, ethylamino, propylamino, hexylamino, etc.), dialkylamino groups having 1 to 6 carbon atoms (eg, dimethylamino, diethylamino, dipropylamino, etc.), 2 to 7 carbon atoms A carbamoyl group (eg, methylcarbamoyl, ethylcarbamoyl, etc.), a sulfamoyl group having 1 to 6 carbon atoms (eg, methylsulfamoyl, ethylsulfamoyl, etc.), or an alkoxycarbonyl group having 2 to 6 carbon atoms (eg, Methoxycarbonyl, ethoxycarbonyl, pentyloxycarbonyl, etc.).

R ₁ , R ₂ , R ₃ , and R ₄ may be the same as or different from each other, and are a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms (eg, methyl, ethyl, propyl,
Butyl, pentyl, hexyl, octyl, 2-chloroethyl, 3-chloropropyl, 2-bromoethyl, 2-hydroxyethyl, cyanomethyl, 2-cyanoethyl, 3
-Cyanopropyl, 2-methoxyethyl, 3-methoxypropyl, 2-ethoxyethyl, 3-ethoxypentyl, 2-isopropoxyethyl, acetylmethyl, 2-
Acetylethyl, benzoylmethyl, acetyloxymethyl, ethylcarbonyloxymethyl, 2,2,2-trifluoroethylcarbonyloxymethyl, isopropylcarbonyloxymethyl, 2- (acetyloxy) ethyl, 2- (2,2,2- Trifluoroethylcarbonyloxy) ethyl, 2- (isopropylcarbonyloxy) ethyl, benzoyloxymethyl, 4-chlorobezoyloxymethyl, 4-nitrobenzoyloxymethyl, acetylaminoethyl, 2- (ethylcarbonylamino) ethyl, methyl Carbamoylmethyl, methylaminoethyl, 2- (ethylamino) ethyl, 2- (dimethylamino) ethyl, 2- (diethylamino) ethyl, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 6-ca Bokishihekishiru, methoxy mosquito Lobo methylpropenylmethyl, ethoxycarbonylmethyl, 2,2,2
Trifluoroethoxycarbonylmethyl, isopropyloxycarbonylmethyl, 3- (isopropoxycarbonyl) propyl, 2- (methoxycarbonyl) ethyl, 2- (ethoxycarbonyl) ethyl, 2- (2.
2,2-trifluoroethoxycarbonyl) ethyl, phenoxycarbonylmethyl, methylsulfonylmethyl,
Ethylsulfonylmethyl, 2- (methylsulfonyl) ethyl, 2- (butylsulfonyl) ethyl, methylsulfonylaminomethyl, 2- (methanesulfonylamino) ethyl, ethanesulfonylaminomethyl, 3- (ethanesulfonylamino) propyl, methylsulfur Famoylethyl, methylaminocarbonylaminoethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 4-
Sulfophenylmethyl, phenylmethyl, etc.), an alkenyl group having 2 to 6 carbon atoms (eg, 3-hexenyl), an unsubstituted or substituted phenyl group (eg, phenyl,
4-chlorophenyl, 4-cyanophenyl, 4-sulfophenyl, 3-sulfophenyl, 4-hydroxyphenyl, 4-carboxyphenyl, 2-methoxyphenyl,
4-methoxyphenyl, 4-ethoxyphenyl, 4-methylphenyl, 4-nitrophenyl, etc.), having 2 carbon atoms
To 7 acyl groups (eg, acetyl, propionyl, heptanoyl, benzoyl, etc.), alkylsulfonyl groups having 1 to 6 carbon atoms (eg, methylsulfonyl, ethylsulfonyl, hexylsulfonyl, etc.), or unsubstituted or substituted phenylsulfonyl groups (For example, phenylsulfonyl, 4-chlorophenylsulfonyl, 4-cyanophenylsulfonyl, 4-sulfophenylsulfonyl,
2-hydroxyphenylsulfonyl, 4-hydroxyphenylsulfonyl, 4-methoxyphenylsulfonyl,
4-methylphenylsulfonyl and the like). Also,
In the case of the compounds of the general formulas (IV) to (VI), R ₁ and R ₂ are 5
A 6-membered ring may be formed. The same applies to R ₃ and R ₄ .

Z ₁ , Z ₂ , Z ₃ , and Z ₄ may be the same or different, and an acyl group having 2 to 13 carbon atoms (for example, acetyl,
Propanoyl, hexanoyl, benzoyl, 4-aminobenzoyl, 4-nitrobenzoyl, 4-methylsulfonylaminobenzoyl, 4-ethylsulfonylaminobenzoyl, 4-propylsulfonylaminobenzoyl,
3-hydroxy-4-methylsulfonylaminobenzoyl, etc., a carbamoyl group having 2 to 13 carbon atoms (for example, methylcarbamoyl group, ethylcarbamoyl group, phenylcarbamoyl group, 4-chlorophenylcarbamoyl group,
4-nitrophenylcarbamoyl, 4-methylsulfonylphenylcarbamoyl, 3-sulfophenylcarbamoyl, 4-propylsulfonylphenylcarbamoyl,
4-propylsulfonylphenylcarbamoyl, 4-methylsulfonylaminophenylcarbamoyl, etc.), a carboxy group, an unsubstituted or substituted alkoxycarbonyl group having 2 to 10 carbon atoms (eg, methoxycarbonyl,
Ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, 1-methylpropoxycarbonyl, t-butoxycarbonyl, chloroethoxycarbonyl, 2,2,2-trifluoroethoxycarbonyl, 3- (hydroxy-n-propoxy) carbonyl. , Cyanoethoxycarbonyl, methoxyethyloxycarbonyl, acetylethyloxycarbonyl,
Acetylaminoethyloxycarbonyl, methylaminoethyloxycarbonyl, dimethylaminoethyloxycarbonyl, carboxyethyloxycarbonyl, methoxycarbonylethyloxycarbonyl, methylsulfonylethyloxycarbonyl, methylsulfonylaminoethyloxycarbonyl, sulfoethoxycarbonyl,
Phenylethoxycarbonyl etc.), an unsubstituted or substituted phenyloxycarbonyl group (eg phenyloxycarbonyl, 4-chlorophenyloxycarbonyl, 4
-Methylphenyloxycarbonyl, 4-methoxyphenyloxycarbonyl, 4-nitrophenyloxycarbonyl, 4-hydroxyphenyloxycarbonyl, 4
-Carboxyphenyloxycarbonyl, 4-cyanophenyloxycarbonyl, 4-dimethylaminophenyloxycarbonyl, 4-methoxycarbonyl, phenyloxycarbonyl group, etc., sulfonyl group having 1 to 12 carbon atoms (for example, methylsulfonyl, ethylsulfonyl, decyl). Sulfonyl, phenylsulfonyl, etc.), sulfamoyl group having 1 to 12 carbon atoms (eg, methylsulfamoyl, ethylsulfamoyl, propylsulfamoyl, phenylsulfamoyl, 4-chlorophenylsulfamoyl, etc.), cyano group Represents an electron-withdrawing group such as. In addition, a ring in which Z ₁ and Z ₂ are linked (for example, a pyrazolone ring, a pyrazolotriazole ring, a pyrazoloimidazole ring, an oxindole ring, an oxindazopyridine ring, an isoxazolone ring, a barbizoleic acid ring, dioxytetrahydropyridine) Ring, indandione ring, etc.) may be formed. The same applies to Z ₃ and Z ₄ .

Z ₅ and Z ₆ may be the same or different and each have a ring (for example, a pyrazolone ring, a pyrazolotriazole ring, a pyrazoloimidazole ring, an oxindole ring, an oxyimidazopyridine ring, an isoxazolone ring, a barbituric acid ring,
Dioxytetrahydropyridine ring, indandione ring, etc.).

Z ₇ and Z ₈ may be the same or different and are an acyl group having 2 to 13 carbon atoms (eg, acetyl, propionyl, heptanoyl, benzoyl, 4-aminobenzoyl, 4-nitrobenzoyl, 4-methanesulfonylaminobenzoyl). , 4-ethanesulfonylaminobenzoyl, 4-propanesulfonylaminobenzoyl, 3-hydroxy-4-methanesulfonylaminobenzoyl, etc.), a carbomoyl group having 2 to 13 carbon atoms (for example, methylcarbamoyl group, ethylcarbamoyl, phenylcarbamoyl). , 4-chlorophenylcarbamoyl, 4-nitrophenylcarbamoyl, 4-methylsulfonylphenylcarbamoyl, 3-sulfophenylcarbamoyl,
4-propylsulfonylphenylcarbamoyl, 4-methylsulfonylaminophenylcarbamoyl, etc.), a carboxy group, an unsubstituted or substituted alkoxycarbonyl group having 2 to 10 carbon atoms (eg, methoxycarbonyl,
Ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, 1-methylpropoxycarbonyl, t-butoxycarbonyl, chloroethoxycarbonyl, 2,2,2-trifluoroethoxycarbonyl, 3-hydroxypropoxycarbonyl,
Cyanoethoxycarbonyl, methoxyethyloxycarbonyl, acetylethyloxycarbonyl, acetylaminoethyloxycarbonyl, methylaminoethyloxycarbonyl, dimethylaminoethyloxycarbonyl, carboxyethyloxycarbonyl, methoxycarbonylethyloxycarbonyl, methylsulfonylethyloxycarbonyl, methane Sulfonylaminoethyloxycarbonyl, sulfoethoxycarbonyl, phenylethoxycarbonyl, etc.), an unsubstituted or substituted phenyloxycarbonyl group (eg phenyloxycarbonyl, 4-chlorophenyloxycarbonyl, 4-methylphenyloxycarbonyl, 4-methoxyphenyloxycarbonyl) , 4-nitrophenyloxycarbonyl,
4-hydroxyphenyloxycarbonyl, 4-carboxyphenyloxycarbonyl, 4-cyanophenyloxycarbonyl, 4-dimethylaminophenyloxycarbonyl, 4-methoxycarbonylphenyloxycarbonyl group, etc.), a sulfonyl group having 1 to 12 carbon atoms ( (Eg, methylsulfonyl, ethylsulfonyl, decylsulfonyl, phenylsulfonyl, etc.), having 1 to 12 carbon atoms
A sulfamoyl group of (for example, methylsulfamoyl,
It represents an electron-withdrawing group such as ethylsulfamoyl, propylsulfamoyl, phenylsulfamoyl, 4-chlorophenylsulfamoyl) and a cyano group.

Y ₁ and Y ₂ are divalent linking groups and have 1 to 1 carbon atoms.
0 unsubstituted or substituted alkylene group (for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, xylylene, bromoethylene, etc.), unsubstituted or substituted arylene group (for example, phenylene group, naphthylene group, chloro) Phenylene group, sulfophenylene group, hydroxyphenylene group, methoxyphenylene group, carboxyphenylene group, methylphenylene group, nitrophenylene group, methanesulfonylaminophenylene group, etc.), carbonyl group, further functional group (for example, oxygen atom, carbonyl group, Amino group, carbonyloxy group, carbonate group, carbonylamino group, ureido group, imide group, sulfonyl group, sulfonyloxy group, sulfonylamino group, sulfonylaminocarbonyl group, etc.) Alkylene group and an arylene group (e.g., _{- (CH 2) 2 -O- (} CH 2) 2 -, - CH 2 COCH 2 -, -CH 2 CO -, - (CH 2) 2 -OCO- (CH 2) 2 -,-(CH ₂ ) ₂ -OCO- (CH ₂ ) ₂ -COO- (CH ₂ ) ₂ -,-(CH ₂ ) ₂ -OCO- (CH ₂ ) ₄ -COO- (CH ₂ ) _2- , -(CH ₂ ) ₂ -OCOO- (CH ₂ ) ₂ -,-(CH ₂ ) ₂ -CONH- (CH ₂ ) ₂ -,-(CH ₂ ) ₂ -NHCONH- (CH ₂ ) ₂ -,-( CH ₂ ) ₂ -CONHCO- (CH ₂ ) ₂ -,-(CH ₂ ) ₂ -SO ₂ NH- (CH ₂ ) ₂ -,-(CH ₂ ) ₂ NHSO ₂ NHCONH (CH ₂ ) ₂ -,-( CH ₂ ) ₂ -SO ₂ NHCO- (CH ₂ ) ₂ -,-(CH ₂ ) ₂ NHSO ₂ NHCO ₂ (CH ₂ ) _2- , -CO- (CH ₂ ) ₂ -CO-, -SO _2- (CH ₂ ) ₄ -SO _2- , -NHSO ₂ (CH ₂ ) ₂ SO ₂ NH-, -O- (CH ₂ ) ₂ -O-, -CONH (CH ₂ ) ₂ NHCO-, -COO (CH ₂ ) ₂ OCO-, -SO ₂ NH (CH ₂ ) ₂ NHSO _2- , -SO ₃ (CH ₂ ) ₂ OSO _2- , Etc.)

Y ₃ and Y ₄ may be the same or different and each is a divalent linking group having an electron withdrawing property, for example, —CO—Y ₅ —.
_{CO-, -SO 2 -Y 5 -SO 2} - , and the like. Where Y ₅ is 2
It is a valent linking group and has an unsubstituted or substituted alkylene group having 2 to 10 carbon atoms (for example, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, xylylene, etc.), an unsubstituted or substituted arylene group (for example, Phenylene group, naphthylene group, chlorophenylene group, sulfophenylene group, hydroxyphenylene group, methoxyphenylene group, carboxyphenylene group,
Methylphenylene group, nitrophenylene group, methanesulfonylaminophenylene group, etc., and further functional groups (for example, oxygen atom, carbonyl group, amino group, carbonyloxy group, carbonate group, carbonylamino group, ureido group, imide group, sulfonyl group) , A sulfonyloxy group,
An alkylene group having a sulfonylamino group, a sulfonylaminocarbonyl group and the like and an arylene group (for example,-(CH ₂ ) _2- O- (CH ₂ ) ₂ -,-(CH ₂ ) _2- OCO- (CH ₂ ) _2- ,-(CH ₂ ) ₂ -OCO- (CH ₂ ) ₂ -COO- (CH ₂ ) ₂ -,-(CH ₂ ) ₂ -OCO- (CH ₂ ) ₄ -COO- (CH ₂ ) _2- , -(CH ₂ ) ₂ -OCOO- (CH ₂ ) ₂ -,-(CH ₂ ) ₂ -CONH- (CH ₂ ) ₂ -,-(CH ₂ ) ₂ -NHCONH- (CH ₂ ) ₂ -,-( CH ₂ ) ₂ -CONHCO- (CH ₂ ) ₂ -,-(CH ₂ ) ₂ -SO ₂ NH- (CH ₂ ) ₂ -,-(CH ₂ ) ₂ NHSO ₂ NHCONH (CH ₂ ) ₂ -,-( CH ₂ ) ₂ -SO ₂ NHCO- (CH ₂ ) ₂ -,-(CH ₂ ) ₂ NHSO ₂ NHCO ₂ (CH ₂ ) _2- , Etc.)

However, in the general formula (III), the divalent linking group Y ₁ is preferably an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms (for example, methylene, ethylene, butylene, etc.), —NH—Y ₆ —NH—, _{-OY 6 -O -, - CONH-} Y 8 -NHCO-, -COO-Y 8 -OCO -, - SO 2 NH-Y 8 -NHSO 2 -, -SO 3 -Y 8 -OSO 2 - is. Here, Y ₆ and Y ₇ are divalent linking groups and have an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms (for example, methylene, ethylene, propylene, butylene, pentylene, hexene, heptylene, octylene, xylylene, Bromoethylene, etc.), an unsubstituted or substituted arylene group (eg, phenylene group, naphthylene group, chlorophenylene group, sulfophenylene group, hydroxyphenylene group, methoxyphenylene group, carboxyphenylene group, methylphenylene group, nitrophenylene group, methylsulfonyl group Aminophenylene group, etc.), carbonyl group, and further functional groups (eg, oxygen atom, carbonyl group, carbonyloxy group, carbonate group, carbonylamino group, ureido group, imide group, sulfonylamino group, sulfonylaminocarbonyl group, etc. Alkylene group and an arylene group (e.g., having a _{- (CH 2) 2 -O- (} CH 2) 2 -, - CH 2 COCH 2 -, -CH 2 CO -, - (CH 2) 2 -OCO- (CH 2 ) ₂ -,-(CH ₂ ) ₂ -OCO- (CH ₂ ) ₂ -COO- (CH ₂ ) ₂ -,-(CH ₂ ) ₂ -OCO- (CH ₂ ) _4- COO- (CH ₂ ) ₂ -, -(CH ₂ ) ₂ -OCOO- (CH ₂ ) ₂ -,-(CH ₂ ) ₂ -CONH- (CH ₂ ) ₂ -,-(CH ₂ ) ₂ -NHCONH- (CH ₂ ) ₂ -,-( CH ₂ ) ₂ -CONHCO- (CH ₂ ) ₂ --(CH ₂ ) ₂ -SO ₂ NH- (CH ₂ ) ₂ -,-(CH ₂ ) ₂ NHSO ₂ NHCONH (CH ₂ ) ₂ -,-(CH ₂ ) ₂ -SO ₂ NHCO- (CH ₂ ) ₂ -,-(CH ₂ ) ₂ NHSO ₂ NHCO ₂ (CH ₂ ) _{2- -CO- (CH 2) 2 -CO -} , - SO 2 - represents the _{like) - (CH 2) 4 -SO} 2.

Y ₈ is a divalent linking group, which is an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms (eg, methylene, ethylene, butylene, etc.), an unsubstituted or substituted arylene group (eg, phenylene group, hydroxyphenylene group, etc.) )
Represents

L represents an unsubstituted or substituted methine group (as a substituent, for example, a methyl group, etc.), and m and n are 0 or 1.

The arylidene bis type dyes represented by the general formulas (I) to (VI) used in the present invention have diffusion resistance due to their bis type structure, and are immobile when incorporated into a gelatin layer of a light-sensitive material as a filter dye or the like. It has a property and can be fixed to a desired layer. Further, the arylidene bis type dye used in the present invention preferably has 2 to 4 sulfo groups or carboxyl groups or salts thereof (preferably alkali metal salts or ammonium salts) in the molecule. Since this sulfo group-containing bis-type dye is hydrophobic while having appropriate hydrophilicity, it can be made water-soluble and can also be dispersed by the so-called "oil-in-water dispersion method". Can be introduced into the material. Further, it shows extremely good decolorizing property when processed with a developing solution containing sulfite. The reason for this is that the addition of sulfite not only erases the color by cutting the conjugated system, but also improves the hydrophilicity associated with the formation of a sulfo group, which causes the bis dye to flow out from the photosensitive material. Conceivable. A bis-type dye having no sulfo group is not sufficient because the hydrophilicity does not become sufficiently high even if the color is once decolorized by the nucleophilic group in the alkaline processing liquid, so that the outflow is not sufficient, and the color reversion occurs in the neutral dry state, which is preferable. Absent.

In the dyes represented by the general formulas (I) and (II) used in the present invention, it is preferable that Z ₁ and Z ₂ or ₃ and Z ₄ are connected to each other to form a pyrazolone ring. The bis type dye having this structure is excellent in decolorization.

Further, in the dye represented by the general formula (I), (II) or (III), Z ₁ and Z ₂ or Z ₃ and Z ₄ may be a combination of a cyano group and an optionally substituted benzoyl group. It is preferable in terms of decolorization during photographic processing.

The compounds represented by the general formulas (I) to (VI) used in the present invention can be synthesized according to the method described in JP-A-51-3623, as shown below, using an aldehyde compound and an active methylene compound. It can be performed by utilizing a condensation reaction.

The synthesis of the compound represented by the general formula (I) or (II) is
It can be obtained by condensing an aldehyde compound represented by the following general formula (VII) or (VIII) and an active methylene (methyl) compound represented by the general formula (IX) or (X).

General formula (VII) General formula (VIII) Formula _{(IX) Z 1 -CH 2 -Z} 2 Formula _{(X) Z 3 -CH 2 -Z} 4 _{However, X 1, X 2, X} 3, X 4, R 1, R 2, Z 1,
Z ₂ , Z ₃ , Z ₄ , Y ₁ , Y ₂ , L, m, and n are as described above.

The condensation reaction is advantageously carried out using a solvent having a property of dissolving the starting material, but many reactions proceed even if the starting material is not dissolved. Suitable solvents include alcohols (eg, methanol, ethanol, isopropanol, etc.), acetonitrile, ethylene gilcol monoalkyl ethers (eg, ethylene glycol monomethyl ether), amides (eg, acetamide, dimethylformamide, etc.) ether. Class (eg,
Dioxane), dimethylsulfoxide, chloroform. These may be used alone or in combination. The reaction is preferably carried out in the temperature range from room temperature to the boiling point of the solvent used, but preferably 50 to 8
It is better to carry out at 0 ° C. To promote the reaction, pyridine, piperidine, diethylamine, triethylamine,
It is advantageous to add an acid such as ammonia gas, potassium acetate, ammonium acetate, acetic acid or a base. The reaction time is usually about 10 minutes to 5 hours.

The compound represented by the general formula (III) has the following general formula (XI)
An aldehyde compound represented by the above general formula (IX),
It can be obtained by condensing the active methylene compound of (X).

General formula (XI) However, X ₁ , X ₂ , R ₁ , R ₂ , R ₃ , R ₄ , Y ₁ ,
L, m, and n are as described above.

This condensation reaction can be carried out under the same conditions as in the case of the compound represented by formula (I) or (II).

Next, the compounds represented by the general formulas (IV) to (VI) are prepared by condensing an aldehyde compound represented by the following general formulas (XII) and (XIII) with an active methylene compound represented by the general formulas (XIV) to (XVI). Can be obtained. This condensation reaction can also be performed under the same conditions as in the case of the compound represented by formula (I) or (II).

General formula (XII) General formula (XIII) General formula (XIV) General formula (XV) General formula (XVI) However, X ₁ , X ₂ , X ₃ , X ₄ , R ₁ , R ₂ , R ₃ ,
R ₄ , Z ₅ , Z ₆ , Z ₇ , Z ₈ , Y ₁ , Y ₃ , Y ₄ ,
L, m, and n are as described above.

Specific examples of the compounds represented by the general formulas (I) to (VI) used in the present invention are shown below. However, the scope of the present invention is not limited to this.

(1) Compound represented by general formula (I) or (II) (2) Compound represented by general formula (III) (3) Compounds represented by general formulas (IV) to (VI) The specific synthesis methods of the representative compounds represented by the general formulas (I) to (VI) used in the present invention are shown below, but other compounds can be synthesized by the same method.

Synthesis Example 1 (Synthesis of Exemplified Compound 1-1) N, N′-biscyanoethyl-N, N′-bis- (4-
Formyl-3-methylphenyl) -1,2-diaminoethane (7.0 g) and cyanoacetic acid (3.0 g) were stirred in acetonitrile (200 ml), and ammonium acetate (3.0 g) was added thereto.
g was added and the mixture was heated to reflux. After 3 hours, the crystals obtained were filtered, washed with acetonitrile and dried. 7.2 g of crystals of Exemplified Compound 1-1 having an absorption maximum wavelength of 392 nm in an aqueous solution and a melting point of 274 to 275 ° C. were obtained.

Synthesis Example 2 (Synthesis of Exemplified Compound 1-13) N, N′-biscyanoethyl-N, N′-bis- (4-
Formylphenyl) -1,2-diaminoethane 16.0
230 g of 3-ethoxy-1- (4-sulfophenyl) pyrazolone sodium salt (26.0 g) with methanol (230 ml)
The mixture was stirred in, 30 ml of acetic acid was added thereto, and the mixture was heated under reflux. The reaction system became uniform in about 1 hour, and then the reaction was continued for about 1 hour. When the reaction solution was cooled to room temperature, crystals were precipitated, and the crystals were filtered, washed with methanol and dried. Absorption maximum wavelength of aqueous solution of 422 nm, exemplary compound 1-
32.1 g of 13 (crystal having a melting point of 300 ° C. or higher) was obtained.

Synthesis Example 3 (Synthesis of Exemplified Compound 1-35) N, N'-biscyanoethyl-N, N'-bis- (4-
Formyl-3-methylphenyl) -1,2-diaminoethane (8.1 g) and 3-ethoxycarbonyl-1- (3-
Sulfopropyl) pyrazolone 9.9 g methanol 15
Stir in 0 ml, to which 5.6 ml triethylamine
And 15 ml of acetic acid were added, and the mixture was heated to reflux. After about 2.5 hours, 150 ml of dimethylformamide was added to make the reaction solution a homogeneous solution. Subsequently, when a solution of 4.0 g of potassium acetate in 20 ml of methanol was added, crystals were precipitated.
The crystals were filtered, washed with ethanol and dried. 12.2 g of Exemplified Compound 1-35 (crystal having a melting point of 187 ° C. (decomposition)) having an absorption maximum wavelength of 486 nm of the aqueous solution was obtained.

Synthesis Example 4 (Synthesis of Exemplified Compound 2-7) 8.0 g of 1,2-bis- {5- (N, N-dicyanoethylamino) -2-formylphenoxy} ethane and 3
9.6 g of -ethoxy-1- (4-sulfophenyl) pyrazolone sodium salt was stirred in 200 ml of methanol, 12 ml of acetic acid was added thereto, and the mixture was heated under reflux for about 2.5 hours. When the reaction solution was cooled to room temperature, crystals were precipitated. The crystals were collected by filtration, washed with methanol and dried.
Absorption maximum wavelength of aqueous solution 412 nm, exemplified compound 2-7
12.1 g of (orange crystal having a melting point of 270 ° C. or higher) was obtained.

Synthesis Example 5 (Synthesis of Exemplified Compound 2-12) 12.0 g of 1,2-bis- {5- (N-dianomethyl-N-methylamino) -2-formylanilino} ethane and 3-ethoxy-1- (4- Sulfophenyl) pyrazolone sodium salt 18.2 g was stirred in 300 ml of methanol until 17 ml of acetic acid and 1 ml of triethylamine.
Was added and the mixture was heated under reflux for about 2 hours. When the reaction solution was cooled to room temperature, crystals were precipitated. The crystals were collected by filtration, washed with methanol and dried. Absorption maximum wavelength 452n of aqueous solution
m, 22.3 g of Exemplified Compound 2-12 (red-orange crystal having a melting point of 270 ° C. or higher) was obtained.

Synthesis Example 6 (Synthesis of Exemplified Compound 3-7) 4-Formyl-N-methyl-N- (2-sulfoethyl)
7.9 g of aniline sodium salt and 1,4-bis- {1
8.0 g of-(4-sulfophenyl) -5-pyrazolone-3-yl} butane was stirred in 180 ml of methanol, and 15 ml of acetic acid and 5 ml of triethylamine were added to about 3
Heated to reflux for hours. Then, 150 ml of water was added to the reaction solution, and dust removal filtration was performed. A methanol solution of 3.7 g of sodium acetate was quickly added to the filtrate, 500 ml of ethanol was further added, and the mixture was allowed to cool to precipitate crystals. The crystals were collected by filtration and washed with ethanol. The crystal was recrystallized from ethanol and water to obtain 10.1 g of Exemplified compound 3-7 (orange yellow crystal). Melting point 300 ° C or higher, 490 nm Synthesis Example 7 (Synthesis of Exemplified Compound 3-22) 66 g of 4-formyl-N-methyl-N- (2-sulfonethyl) aniline sodium salt and 1,2-bis-
5.0 g of [{4- (cyanoacetyl) phenyl} aminocarbonyl] ethane was stirred in 300 ml of methanol, 10 drops of piperidine was added thereto as a catalyst, and the mixture was heated under reflux for about 5 hours. After allowing the reaction solution to cool to room temperature, crystals were collected by filtration. The crystals were recrystallized from methanol and water to give Exemplified Compound 3-22 (6.8 g of orange-yellow crystals. Melting point 30.
0 ℃ or more, 452 nm When the dyes represented by the general formulas (I) to (VI) are used as a filter dye, an anti-irradiation dye or an antihalation dye, any effective amount can be used, but an optical density of 0.05 to , 3.0 is preferably used. The addition time may be any step before coating. The amount of dye applied is usually
0.001 to 1 g / m ² preferably 0.001 to 0.5 g
/ M ² .

The dye according to the present invention can be dispersed in a hydrophilic colloid layer such as an emulsion layer (intermediate layer, protective layer, antihalation layer, filter layer, etc.) by various known methods.

A method of directly dissolving or dispersing the dye of the present invention in an emulsion layer or a hydrophilic colloid layer, or a method of dissolving or dispersing it in an aqueous solution or a solvent and then using it in the emulsion layer or the hydrophilic colloid layer. Suitable solvents such as methyl alcohol, ethyl alcohol, propyl alcohol, methyl cellosolve, JP-A-48-9715, US Pat.
It can also be added to the emulsion in the form of a solution dissolved in a halogenated alcohol described in No. 6,830, acetone, water, pyridine, or a mixed solvent thereof.

A method in which a compound obtained by dissolving a compound in oil, that is, a high-boiling point solvent that is substantially insoluble in water and has a boiling point of about 160 ° C. or higher is added to a hydrophilic colloidal solution and dispersed. Examples of the high boiling point solvent include, for example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate) as described in US Pat. No. 2,322,027. , Tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (eg tributyl acetyl citrate), benzoic acid esters (eg octyl benzoate), alkylamides (eg diethyllaurylamide), fatty acid esters (eg dibutoxy). Ethyl succinate, diethyl azelate), trimesic acid esters (eg tributyl trimesic acid) and the like can be used. Also, the boiling point is about 30 ° C to about 150 ° C.
Organic solvents, for example, lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, and solvents that are easily soluble in water, such as methanol and Alcohol such as ethanol can also be used.

Here, the usage ratio of the dye and the high boiling point solvent is 10 to 1
/ 10 (weight ratio) is preferable.

A method of incorporating the dye and other additives of the present invention as a polymer latex composition filled with a photographic emulsion layer or other hydrophilic colloid layer.

Examples of the polymer latex include polyurethane polymers, polymers polymerized from vinyl monomers [suitable vinyl monomers include acrylic acid esters (methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate,
Dodecyl acrylate, glycidyl acrylate, etc.),
α-substituted acrylic ester (methyl methacrylate,
Butyl methacrylate, octyl methacrylate, glycidyl methacrylate, etc.), acrylamide (butyl acrylamide, hexyl acrylamide, etc.), α-substituted acrylamide (butyl methacrylamide, dibutyl methacrylamide, etc.), vinyl ester (vinyl acetate, vinyl butyrate, etc.), vinyl halide , (Vinyl chloride, etc.),
Vinylidene halide (vinylidene chloride, etc.), vinyl ether (vinyl methyl ether, vinyl octyl ether, etc.), styrene, X-substituted styrene (α-methylstyrene, etc.), nucleus-substituted styrene (hydroxystyrene, chlorostyrene, methylstyrene, etc.), Examples thereof include ethylene, propylene, butylene, butadiene and acrylonitrile. These may be used alone or in combination of two or more, or may be mixed with other vinyl monomer as a minor component. Other vinyl monomers include itaconic acid, acrylic acid, methacrylic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, sulfoalkyl acrylate, sulfoalkyl methacrylate, styrene sulfonic acid, and the like. ] Etc. can be used.

These filled polymer latexes are disclosed in Japanese Examined Patent Publication No. 51-398.
53, JP-A-51-59943, and JP-A-53-1371.
No. 31, No. 54-32552, No. 54-107941
No. 55-133465, No. 56-19043,
56-19047, 56-126830, 5
It can be manufactured according to the method described in JP-A-8-149038.

The ratio of dye and polymer latex used is 1
0 to 1/10 (weight ratio) is preferable.

A method in which a hydrophilic polymer having a charge opposite to that of a dye ion coexists in a layer as a mordant, and the dye is localized in a specific layer by interacting with the dye molecule.

The polymer mordant is a polymer having a nitrogen-containing heterocyclic moiety containing a secondary or tertiary amino group, and a polymer having a quaternary cation group or the like having a molecular weight of 5,000 or more, particularly preferably 10,000 or more.

For example, vinyl pyridine polymers and vinyl pyridinium cationic polymers described in US Pat. No. 2,548,564; vinyl imidazolium cationic polymers disclosed in US Pat. No. 4,124,386; US patents. Polymer mordanting agents capable of crosslinking with gelatin and the like disclosed in 3,625,694 and the like; aqueous sol type dyeing agents disclosed in U.S. Pat. No. 3,958,995 and JP-A-54-115228. Water-insoluble mordants disclosed in U.S. Pat. No. 3,898,088; Reactive mordants capable of forming a covalent bond with the dyes disclosed in U.S. Pat. No. 4,168,976; British Patent 685. Derived from ethylenically unsaturated compounds having dialkylaminoalkyl ester residues as described in US Pat. Rimmer; British Patent 850,281
A product obtained by the reaction of a polyvinyl alkyl ketone with aminoguanidine as described in US Pat. No. 3,445,231;
Mention may be made of polymers derived from methyl-1-vinylimidazole.

A method of dissolving a compound using a surfactant.

The useful surfactant may be an oligomer or a polymer.

For details of this polymer, see Japanese Patent Application No. 59-12766.
No. (Fuji Photo Film Co., Ltd. January 26, 1984)
(Filed by date) on pages 19-27.

The method of using a hydrophilic polymer in place of the high boiling point solvent or in combination with the high boiling point solvent. Regarding this method, for example, US Pat. No. 3,619,195 and West German Patent 1,9
57,467.

A microcapsule method using a polymer having a carboxyl group, a sulfonic acid group or the like in its side chain as described in JP-A-59-113434.

Further, a hydrosol of a lipophilic polymer described in JP-B-51-39835 may be added to the hydrophilic colloid dispersion obtained above.

Gelatin is a typical hydrophilic colloid, but any of those conventionally known as those usable for photography can be used.

The silver halide emulsion usable in the present invention may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride. Preferred silver halides are silver bromide, silver chlorobromide, silver iodobromide or silver iodochlorobromide.

The silver halide grains in the photographic emulsion layer may have regular crystal bodies such as cubes and octahedra, and irregular grains such as spheres and plates.
It may have a different crystal form or a composite form of these crystal forms. It may consist of a mixture of particles of various crystal forms.

The silver halide grains may have different phases in the inside and the surface layer, or may be composed of a uniform phase. Also, grains in which a latent image is mainly formed on the surface (eg negative emulsion).
Alternatively, it may be a grain that is mainly formed inside the grain (for example, an internal latent image type emulsion, a direct inversion type emulsion which has been fogged in advance).

The silver halide emulsion used in the present invention has a thickness of 0.5 micron or less, preferably 0.3 micron or less, a diameter of preferably 0.6 micron or more, and an average aspect ratio of 5 or more. The tabular grains may occupy 50% or more of the area. Further, it may be a monodisperse emulsion in which grains having a grain size within ± 40% of the average grains account for 95% or more of the number of grains.

The photographic emulsion used in the present invention is pea. Graf Kiddes (P.
Glafkides), Chimie er Physique Photogroheque (Ball Montel, 1967), Gee. F. GF Duffin, Phtograpic Emulsion Chemistry (Focal Press, 1966), VL Zelikman et al., Making and Coating Photographic Emulsion (Making)
and Coating Photographic Emulsion) (Focal Press, 1964) and the like.

Further, at the time of forming the silver halide grains, as a silver halide solvent for controlling grain growth, for example, ammonia, rhodancali, rhodammone, and thioether compound (for example, US Pat. Nos. 3,271,157 and 3,574, 3,574, No. 628, No. 3,704,130, No. 4,297,439, No. 4,276,374, etc.) and thione compounds (for example, JP-A-53-144319).
No. 53-82408, No. 55-77737, etc.), amine compounds (for example, JP-A-54-10071).
No. 7, etc.) and the like can be used.

In the process of silver halide grain formation or physical ripening,
Cadmium salt, zinc salt, thallium salt, iridium salt or complex salt thereof, rhodium salt or complex salt thereof, iron salt or iron complex salt may be allowed to coexist.

Silver halide emulsions are usually chemically sensitized. For chemical sensitization, for example, H. Freesel (H.Frieser) edition,
Die Grundlagen Del Photography Sien Protese Mitt Gilberhalogeniden (Die
Grundlagen der PhotographischenProzesse mitSilberh
alogenden) (Academia Michel Ferragus Gezerschact 1968) pp. 675-734 can be used.

That is, a sulfur sensitization method using a compound containing sulfur capable of reacting with active gelatin or silver (for example, thiosulfate, thioureas, mercapto compounds, rhodanins); a reducing substance (for example, first tin salt, Reduction sensitization method using amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds); using noble metal compounds (for example, complex salts of metals of Group VIII of the Periodic Table such as Pt, Ir, Pd in addition to gold complex salts) The noble metal sensitization method and the like can be used alone or in combination.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted compounds), heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, Mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; a thioketo compound For example, oxazoline thione; azaindenes such as tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes); benzenethiosulfo Acids; benzenesulfinic acid; many compounds known to the antifoggants or stabilizers, such as can be added.

The silver halide photographic emulsion of the present invention is a color coupler such as a cyan coupler, a magenta coupler and a yellow coupler.
A coupler and a compound that disperses the coupler may be included.

That is, it may contain a compound capable of forming a color by oxidative coupling with an aromatic primary amine developing agent (for example, a phenylenediamine derivative or an aminophenol derivative) in the color development processing. For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, closed acylacetonitrile couplers, and the like, and yellow couplers include acylacetamide couplers (for example, benzoylacetanilides, pivaloylacetanilides). , Etc., and cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible ones having a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent with respect to silver ion. Further, a colored coupler having a color correction effect or a coupler releasing a development inhibitor with development (so-called D
IR coupler).

In addition to the DIR coupler, a non-coloring DIR coupling compound which is colorless in the product of the coupling reaction and releases a development inhibitor may be contained.

The photographic emulsions of the present invention include polyalkylene oxide or its derivatives such as ethers, esters and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds and urethane derivatives for the purpose of increasing sensitivity, increasing contrast or promoting development. , Urea derivatives, imidazole derivatives, 3-pyrazolidones and the like.

In the silver halide photographic emulsion of the present invention, known water-soluble dyes other than the dyes disclosed in the present invention (for example, oxonol dyes; hemioxonol dyes and merocyanine dyes) are used as filter dyes or for various purposes such as prevention of irradiation. ) And may be used in combination. Further, as a spectral sensitizer, a known cyanine dye, merocyanine dye, or hemicyanine dye other than the dyes shown in the present invention may be used in combination.

The photographic emulsion of the present invention contains various surfactants for various purposes such as coating aid, antistatic property, sliding property improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration, hardening, sensitization). But it's okay.

Regarding the light-sensitive material of the present invention, with respect to anti-fading agent, hardener, anti-foggant, ultraviolet absorber, protective colloid such as gelatin, and various additives, specifically, Research Disclosure Vol. 176 ( 1978, XII) RD-
17643 and the like.

The finished emulsion is coated on a suitable support such as baryta paper, resin coated paper, synthetic paper, triacetate film, polyethylene terephthalate film, other plastic bases or glass plates.

The silver halide photographic light-sensitive material of the present invention includes a color positive film, a color paper, a color negative film, a color reversal film (which may or may not contain a coupler), and a plate-making photographic light-sensitive material (for example, lith film, lith dupe). Film, etc.), photosensitive materials for cathode ray tube displays (eg emulsion X-ray recording photosensitive materials, direct and indirect imaging materials using screens), silver salt diffusion transfer process photosensitive materials, color diffusion transfer Photosensitive material for process, photosensitive material for die transfer process, emulsion for silver dye bleaching method, photosensitive material for recording printout image, photo-developing printout (Direct Print
image) Photosensitive materials, photothermographic materials, and physical development photosensitive materials.

The exposure for obtaining a photographic image may be performed using a usual method. That is, any of various known light sources such as natural light (sunlight), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, and cathode ray tube flying spot can be used. The exposure time is usually less than 1/1000 second, which is usually used in a camera, and less than 1/1000 second.
For example, 1/10 ⁴ using a xenon flashlight or cathode ray tube
Exposures of up to 1/10 ⁶ seconds can be used or exposures longer than 1 second can be used. The spectral composition of the light used for exposure can be adjusted with a color filter as needed. Laser light can also be used for the exposure. Further, it may be exposed by light emitted from a phosphor excited by an electron beam, X-ray, γ-ray, α-ray or the like.

Photographic processing of a light-sensitive material produced by using the present invention includes, for example, Research Disclosur (Research Disclosur).
e) Any known method and known processing solution as described in 176, pp. 28-30 (RD-17643) can be applied. This photographic processing may be either photographic processing for forming a silver image (black and white photographic processing) or photographic processing for forming a dye image (color photographic processing) depending on the purpose. The treatment temperature is usually chosen between 18 and 50 ° C, but it may be below 18 ° C or above 50 ° C.

According to the present invention, a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a novel dye which has a proper spectral absorption and selectively dyes a specific layer and does not diffuse to other layers is obtained. You can

Further, according to the present invention, a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a novel dye that is decolorized in photographic processing and does not adversely affect the photographic characteristics of a photographic emulsion, particularly the spectral sensitization property, is obtained. You can

Furthermore, according to the present invention, a silver halide photographic light-sensitive material having excellent stability over time can be obtained.

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail based on examples.

The performance test method performed in the examples is as follows.

1) Relative sensitivity: The reciprocal of the exposure amount that gives a density of 1.5. The case where no dye is added (Samples 1, 19 and 60) is 100.

EX ₁ ; exposure amount giving density 0.3 EX ₂ ; exposure amount giving density 3 3) Fog after safelight irradiation: Toshiba fading prevention fluorescent lamp (FLR40SW-DL-XNu)
/ M) Fog when developed after irradiation for 1 hour under about 200 lux.

4) Residual color: λmax absorbance after development Example 1 A silver halide emulsion composed of silver chlorobromide (5 mol% of silver bromide average particle size: 0.25 μ) containing 1 × 10 ⁻⁵ mol of Rh per 1 mol of silver was prepared.

This emulsion was divided into 9 parts, to each of which was added 2-hydroxy-4,6-dichloro-1,3,5-triazine sodium as a hardener and potassium polystyrene sulfonate as a thickener, and the mixture was placed on a polyethylene terephthalate film. The amount of silver applied was 4 g / m ² . This 9
As a protective layer on one emulsion layer, a gelatin solution containing or not containing the dyes shown in Table 1 was used at a gelatin amount of 1.0.
It was applied so as to be g / m ² . Sodium p-dodecylbenzenesulfonate was used as a coating aid for this protective layer, and the same compound as that for the emulsion layer was used as a thickener.

The sample thus obtained was exposed with a P-607 type printer manufactured by Dainippon Screen Co., Ltd. through an optical wedge, and then developed with a developing solution LD-835 manufactured by Fuji Photo Film Co., Ltd.

The results are shown in Table 1.

Comparative compound A (described in US Pat. No. 3,002,837) Comparative compound B Comparative compound C As is clear from the results shown in Table 1, in Samples 7 to 9, most of the dyes added to the protective layer diffuse into the emulsion layer, and safelight safety can be obtained, but the decrease in γ is remarkable. Sample 9 has almost no diffusion into the emulsion layer, but has a problem of significant residual color. On the other hand, in Samples 2 to 6 of the present invention, the dye added to the protective layer did not diffuse into the emulsion layer, and the decrease in γ was very small, and the safelight safety was improved. Also, there is almost no residual color.

Example 2 5 g of Exemplified Compound 1-13 was dispersed and dissolved in 100 ml of water, 250 g of 14% gelatin solution was mixed, and the mixture was stirred using a colloid mill. This composition was coated on a cellulose triacetate film support at a coating amount of 8 g / m ² to obtain Sample 10.

Then, instead of the exemplified compound 1-13, the exemplified compound 1-4
Samples were prepared in the same manner using 0, 1-14, 1-15, and 1-77, and samples 11 to 14 were prepared. Further, samples 15 to 17 were prepared in the same manner as above using the comparative compounds A, B, D and E. Furthermore, Exemplified Compound 1-13
When mixing an aqueous solution of the compound with a gelatin solution, tricresyl phosphate (dye / oil ratio =
1), ethyl acetate, and sodium p-dodecylbenzenesulfonate as an emulsifier were added and emulsified and dispersed to obtain a sample 19.

Sample 20 was prepared by similarly dispersing and applying polyethyl acrylate (dye / polymer ratio = 1) in place of tricresyl phosphate of Sample 19.

Each sample thus obtained was cut into 5 cm ² , and its visible absorption spectrum was measured. The sample is then 38
It was washed with water (20 ml) for 3 minutes at ℃. After the sample was dried, the spectrum was measured again, and the dyeing property of the dye was evaluated according to the following formula.

The decolorizing property was evaluated by immersing the prepared sample (5 cm ² ) in a treatment liquid having the following composition at 38 ° C. for 3 minutes, washing with water and drying, and then measuring the spectrum.

H ₂ O 10000cc Metol 2g Hydroquinone 5g Sodium sulfite 70g Calcium carbonate 40g Potassium bromide 2g The results obtained are shown in Table 2.

Comparative compound D Comparative compound E (described in US Pat. No. 3,389,994) As is clear from the results in the above table, all of the samples used in the present invention are stable even when washed with water and have sufficient dyeability, and by being subjected to a treatment, a substantially complete decolorizing property is obtained. Show.

Further, as can be seen from the results of Sample 19, even when the dye of the present invention is emulsified and dispersed, excellent dyeing property and decoloring property are similarly exhibited.

Example 3 Silver chlorobromide containing 0.8 × 10 ⁻⁵ mol of Rh per 1 mol of silver (average particle size containing 5 mol% of silver bromide; 0.23 μ)
Was prepared.

The emulsion was divided into 11 parts, the same compounds as in Example 1 were added as a hardener and a thickener, and the resulting mixture was coated on a polyethylene terephthalate film so that the amount of silver was 3.8 g / m ² . On this emulsion layer, zerain (amount of 1 g / m ² ),
The following mordants (amount of 0.05 g / m ² ) and third
Various dyes shown in the table were dissolved in water and then applied as a protective layer. As the coating aid, the same compounds as in Example 1 were used.

mordant The sample thus obtained was treated in the same manner as in Example 1 and tested for relative sensitivity, γ, fog after safelight irradiation, and residual color in the same manner as in Example 1.

The results are shown in Table 3.

As is clear from the results in Table 3, by using the dye together with the mordant in the present invention, the diffusion of the dye into the emulsion layer is further reduced as compared with the dye alone, and the decrease of γ is further prevented, and the safe light The safety can be improved.

Example 4 To a 5% gelatin aqueous solution, the dyes shown in Table 4 were added, and the same hardening agents, thickeners and coating aids as in Example 1 were added, and 3 g / m of gelatin was added on the polyethylene terephthalate film. ² and the dye was applied so as to be 0.25 mmol / m ² .

The sample thus obtained was bashed in water at 40 ° C. for 5 minutes to examine the dyeing property of the dye.

Further, the same sample was subjected to a developing treatment in the same manner as in Example 1 to examine the residual color property.

The results are shown in Table 4.

Comparative compounds F, G, H and I As is clear from the results in Table 4, Samples 32 to 5 of the present invention
It can be seen that No. 7 has almost no residual color in the development process and has excellent dyeability to gelatin.

Example 5 Silver chlorobromide containing 0.9 × 10 ⁻⁵ mol of Rh per 1 mol of silver (contains 4 mol% of silver bromide; average particle size: 0.2
5 μ) was prepared as a silver halide emulsion.

This emulsion was divided into 6 parts and used as a hardener and a thickener in Example 1.
A compound similar to the above was added and coated on polyethylene terephthalate so that the amount of silver was 4 g / m ² .

A gelatin solution containing various dyes shown in Table 5 as a protective layer was coated on the emulsion layer so that the amount of gelatin was 1.0 g / m ² . As the coating aid and thickener for this protective layer, the same compounds as in Example 1 were used.

The sample thus obtained was developed in the same manner as in Example 1.

The results are shown in Table 5.

As is clear from the results in Table 5, Samples 63 to 63 of the present invention
In No. 65, even when two kinds of dyes were added to the protective layer, the diffusion to the emulsion layer was small, the decrease in γ and the residual color were small, and the safelight safety was improved.

Example 6 On a polyethylene terephthalate film support, a multi-layer color light-sensitive material sample composed of each layer having the composition shown below was prepared.

1st layer: Antihalation layer Gelatin layer containing black colloidal silver 2nd layer: Intermediate layer Gelatin layer containing emulsified dispersion of 2,5-di-t-octylhydroquinone 3rd layer; 1st red sensitive emulsion layer Iodour Silver halide emulsion (silver iodide; 5 mol%) ... Silver coating amount 1.6 g / m ² Sensitizing dye I ... 4.5 × 10 ^-4 mol Sensitizing dye II per 1 mol of silver・ ・ 1.5 × 10 ^-4 mol for 1 mol of silver Coupler C-1 ・ ・ ・ ・ 0.4g / m ² Coupler C-2 ・ ・ ・ ・ 0.03g / m ² Coupler C-3 ・ ・ ・ ・ 0.02g / m ² 4th layer; 2nd red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 6 mol%) ... Silver coating amount 1.0 g / m ² Sensitizing dye I ... Silver 1 mol To 3 × 10 ⁻⁴ mol Sensitizing dye II ··· 1 mol of silver 1 × 10 ⁻⁴ mol Coupler C-1 ··· 0.03 g / m ² coupler C-4 ··· 0.03 g / m ² coupler ^C-2 ···· 0.01g / m 2 layer 5: intermediate layer second layer and Flip sixth layer; to .... silver coverage 0.9 g / m ² sensitizing dye III ... 1 mol of silver; the first green-sensitive emulsion layer silver iodobromide emulsion (4 mol% iodide) 5 × 10 ^-4 moles Sensitizing dye IV ... 1 mole of silver 1 × 10 ^-4 moles Coupler C-5 ... 0.04 g / m ² Coupler C-6 ... 0.15 g / m ² coupler C-3 ... 0.05g / m ² 7th layer; 2nd green sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 6 mol%) .... Silver coating amount 1.1g / m ² Sensitizing dye III ・ ・ ・ ・ ・ ・ 3 × 10 ^-4 mol to 1 mol of silver Sensitizing dye IV ・ ・ ・ ・ 1.2 × 10 ^-4 mol to 1 mol of silver Coupler C-7 ・ ・ ・ ・0.01g / m ² coupler C-8 ... 0.07g / m ² coupler C-6 ... 0.02g / m ² 8th layer; yellow filter layer Yellow colloidal silver and 2,5- J-t
-Gelatin layer containing octylhydroquinone emulsified dispersion Yellow colloidal silver Silver coating amount 0.08 g / m ² 9th layer; 1st blue sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 4 mol%) ...・ Silver coating amount 0.4g / m ² Sensitizing dye V ・ ・ ・ ・ 2 × 10 ^-4 mol coupler C-9 ・ ・ ・ ・ ・ ・ 0.9g / m ² coupler C-3 ・ ・ ・ ・ for 1 mol of silver 0.05 g / m ² 10th layer: second blue-sensitive emulsion layer silver iodobromide (silver iodide: 6 mol%) ... silver coverage 0.6 g / m ² sensitizing dye V ... Ag 1 × 10 ⁻⁴ mol per mol Coupler C-9 ... 0.25 g / m ² 11th layer; 1st protective layer Gelatin layer containing emulsion product of UV absorber UV-1 12th layer; 2 Protective layer A gelatin layer containing polymethylmethacrylate particles (diameter about 1.5 μ).

In addition to the above composition, a gelatin hardening agent H-1 and a surfactant were added to each layer. The sample produced as described above was designated as Sample 68.

Instead of the yellow colloidal silver in the eighth layer of Sample 68, an emulsion prepared by a method similar to that of Example 1 except that Exemplified Compound 1-13 was prepared, was coated with Compound 1-13 at a coating amount of 0.2 g / m ^2.
Sample 69 was prepared in the same manner as sample 68 except that the sample was coated so that A sample prepared in the same manner using Comparative Compound C was designated as 70. The eighth of sample 68
The sample excluding the yellow colloidal silver of the layer was made, and this was sample 7
It was set to 1.

The compounds used for the sample preparation are as follows.

Sensitizing dye I Sensitizing dye II Sensitizing dye III Sensitizing dye IV Sensitizing dye V The samples 68, 69 and 70 thus obtained were subjected to wedge exposure by a conventional method and subjected to the following development processing.

Samples 68 to 71 were prepared by preparing a processing solution in which 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate was removed from the color developing solution in the following processing step.
And the following steps 2 to 6 were performed to evaluate the decolorizing property of the dye.

The difference between the yellow density of each of Samples 68 to 70 and the yellow density of Sample 71 was defined as ΔD ^B min.

The results obtained are shown in Table 6.

The development process used here was carried out at 38 ° C. as described below.

 1. Color development: 3 minutes 15 seconds 2. Bleaching: 6 minutes and 30 seconds 3. Washing with water ・ ・ ・ 3 minutes 15 seconds 4. Fixed arrival: 6 minutes and 30 seconds 5. Washing with water ・ ・ ・ 3 minutes 15 seconds 6. Stabilization: 3 minutes 15 seconds The composition of the treatment liquid used in each process is as follows.

Color developer Sodium nitrilotriacetate 1.0 g Sodium sulfite 4.0 g Sodium carbonate 30.0 g Potassium bromide 1.4 g Hydroxylamine sulfate 2.4 g 4- (N-ethyl-N-β-hydroxyethylamino) -2 -Methylaniline sulfate 4.5 g Water added 1 Bleach Ammonium bromide 160.0 g Ammonia water (28%) 25.0 cc Ethylenediamine-sodium tetraacetate iron salt 130.0 g Glacial acetic acid 14.0 cc Water added 1 Fixer Sodium tetrapolyphosphate 2.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (70%) 175.0 cc Sodium bisulfite 4.6 g Water was added 1 Stabilizer Formalin 8.0 cc Water was added 1 The sample 69 according to the present invention has a ΔD ^B min value of 0, and there is no problem in decolorization of the dye due to the treatment. In addition, the degree of fogging is lower than when yellow colloidal silver is used, and desensitization is less when yellow colloidal silver is used. In Comparative Sample 70, the dyeing property is not sufficient and the dye diffuses to the other layers, which causes a significant desensitization.

Regarding Samples 68 and 69, the samples were left for 1 month under the condition of 35 ° C. and 70% RH to examine the stability over time.
In comparison with 68, it was revealed that changes in fog and sensitivity in the blue-sensitive layer and the green-sensitive layer were small.

Example 7 A color reversal photographic material, Sample 72, was prepared by coating the first to twelfth layers in the following order on a cellulose triacetate film support.

First layer: Antihalation layer Gelatin layer containing black colloidal silver Second layer: Intermediate layer Gelatin layer containing emulsified dispersion of 2,5-di-t-octylhydroquinone Third layer: First red-sensitive emulsion layer Odor Silver iodide (silver iodide; 6 mol%) Silver coating amount 0.5 g / m ² Coupler C-10 0.4 g / m ² 4th layer; Second red-sensitive emulsion layer Silver iodobromide (silver iodide; 6 mol%) ) Silver coating amount 0.8 g / m ² coupler C-10 0.9 g / m ² 5th layer; intermediate layer Gelatin layer containing emulsified dispersion of 2,5-di-t-octylhydroquinone 6th layer; 1st green feeling Emulsion layer Silver iodide Silver coating amount 1g / m ² Coupler C-11 0.4g / m ² 7th layer; 2nd green sensitive emulsion layer Silver iodobromide 1.1g / m ² Coupler C-11 0.9g / m ^2nd 8 layers; yellow filter layer Yellow colloidal silver and 2,5-di-t in gelatin aqueous solution
-Gelatin layer containing octyl hydroquinone emulsified dispersion Yellow colloidal silver Silver coating amount 0.08 g / m ² 9th layer; First blue sensitive emulsion layer Silver iodobromide Silver coating amount 0.4 g / m ² Coupler C-12 0.5 g / m ² 10th layer; 2nd blue sensitive emulsion layer Silver iodobromide Silver coating amount 0.8g / m ² Coupler C-12 0.95g / m ² 11th layer; 1st protective layer UV absorber UV-1 Gelatin layer containing emulsified dispersion 12th layer; 2nd protective layer Surface-fogged fine grain emulsion (particle size 0.6μ, 1
Gelatin layer containing mol% silver iodobromide emulsion) and polymethylmethacrylate particles (diameter about 1.5μ). Then, in place of the yellow colloidal silver of the eighth layer of sample 72, Exemplified Compounds 1-14 were prepared in Example 1. The emulsion prepared in the same manner as described above was coated with Compound 1-14 at a coating amount of 0.2.
A sample 73 was prepared in the same manner as the sample 72 except that the coating was performed so that the coating amount was g / m ² .

The compounds used for the sample preparation are as follows.

The obtained sample was subjected to wedge exposure with white light and then subjected to the following reversal processing.

The development process used here was carried out at 38 ° C. as described below.

 1. First development: 6 minutes 2. Washing with water ... 2 minutes 3. Inversion ... 2 minutes 4. Color development: 6 minutes 5. Adjustment ... 2 minutes 6. Bleaching ... 6 minutes 7. Set-up: 4 minutes 8. Washing with water ... 4 minutes 9. Stabilization: 1 minute Use the following composition of the processing solution.

First developer water 700 ml sodium tetrapolyphosphate 2 g sodium sulfite 20 g hydroquinone monosulphonate 30 g sodium carbonate (monohydrate) 30 g 1-phenyl-4-methyl-4-hydroxymethyl-3pyrazolidone 2 g potassium bromide 2.5 g thiocyan Potassium acidate 1.2 g Potassium iodide (0.1% solution) 2 ml Water was added to 1000 ml (PH10.1) Inversion solution water 700 ml Nitro-NNN-trimethylene osmethylene acid 6Na salt 3 g Stannous chloride ( Dihydrate) 1 g p-aminophenol 0.1 g sodium hydroxide 8 g glacial acetic acid 15 ml Water is added to 1000 ml Color developer water 700 ml Sodium tetrapolyphosphate 2 g Sodium sulfite 7 g Sodium triphosphate (12 hydrate) 36 g Bromide Cali 1 g potassium iodide (0.1% solution) 90 ml sodium hydroxide 3 g citrazinic acid 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 11 g ethylenediamine 3g Water was added 1000ml Adjusted water 700ml Sodium sulfite 12g Ethylenediamine, sodium tetraacetate (dihydrate) 8g Thioglycerin 0.4ml Glacial acetic acid 3ml Water was added 1000ml Bleached water 800g Ethylenediaminetetraacetate sodium (dihydrate) 2.0g Ethylenediaminetetraacetic acid Iron (III) ammonium (dihydrate) 120.0g Potassium bromide 100.0g Water added 1000ml Fixer water 800g Ammonium thiosulfate 80.0g Sodium sulfite 5.0g Bisulfite Sodium acid 5.0 g Water added 1000 ml Stabilized water 800 ml Formalin (37% by weight) 5.0 ml Fuji Drywell 5.0 ml Water added 1000 ml Sample 73 according to the present invention has good decolorization by treatment. The stain in the highlight part was also equivalent to that of Sample 72.

Further, since the fog value due to the first development of the adjacent emulsion layers was low, the maximum density in the reversal image was increased by 22% in yellow and 11% in magenta as compared with Sample 72.

Therefore, it is understood that the film thickness of the emulsion layer can be further reduced by using the dye of the present invention.

Example 8 A silver halide emulsion composed of silver chlorobromide (5 mol% of silver bromide average grain size: 0.25 μ) containing 1 × 10 ⁻⁵ mol of Rh per 1 mol of silver was prepared.

This emulsion was divided into 9 parts, to each of which was added 2-hydroxy-4,6-dichloro-1,3,5-triazine sodium as a hardener and potassium polystyrene sulfonate as a thickener, and the mixture was coated on a polyethylene terephthalate film. It was coated so that the amount of silver was 4 g / m ² . A gelatin solution containing or not containing the dyes shown in Table 7 was used as a protective layer on the nine emulsion layers in an amount of 1.0 g.
It was applied so as to be / m ² . Sodium p-dodecylbenzenesulfonate was used as a coating aid for this protective layer, and the same compound as that for the emulsion layer was used as a thickener.

The sample thus obtained was exposed with a P-607 type printer manufactured by Dainippon Screen Co., Ltd. through an optical wedge, and then developed with a developing solution LD-835 manufactured by Fuji Photo Film Co., Ltd.

The results are shown in Table 7.

Comparative compound A Comparative compound B Comparative compound C As is clear from the results in Table 7, in Samples 7 and 8, most of the dyes added to the protective layer diffuse into the emulsion layer, and safelight safety can be obtained, but the decrease in γ is remarkable. Sample 9 has almost no diffusion into the emulsion layer, but has a problem of significant residual color. On the other hand, in Samples 2 to 6 of the present invention, the dye added to the protective layer did not diffuse into the emulsion layer, and the decrease in γ was very small, and the safelight safety was improved. Also, there is almost no residual color.

Example 9 Silver chlorobromide containing 0.9 × 10 ⁻⁵ mol of Rh per 1 mol of silver (average particle size containing 5 mol% of silver bromide; 0.22 μ)
Was prepared.

This emulsion was divided into 7 parts and used as a hardener and a thickener in Example 8.
A compound similar to the above was added and coated on a polyethylene terephthalate film so that the amount of silver was 3.8 g / m ² . Gelatin (1 g / m ² ) on this emulsion layer,
The mordant shown below (amount to be 0.5 g / m ² ) and various dyes shown in Table 8 were dissolved in water and then applied as a protective layer.
As the coating aid, the same compound as in Example 8 was used.

mordant The sample thus obtained was treated in the same manner as in Example 1 and tested for relative sensitivity, γ, fog after safelight irradiation, and residual color in the same manner as in Example 1.

The results are shown in Table 8.

As is clear from the results in Table 8, by using the dye in combination with the mordant in the present invention, the diffusion of the dye into the emulsion layer is further reduced as compared with the dye alone, and the decrease of γ is further prevented. The safety can be improved.

Example 10 The dyes shown in Table 9 were added to a 5% gelatin aqueous solution, and the same hardening agents, thickeners and coating aids as in Example 8 were added, and 3 g / g of gelatin was added onto the polyethylene terephthalate film. m ² and the dye were applied so as to be 0.25 mmol / m ² .

The sample thus obtained was bashed in water at 40 ° C. for 5 minutes to examine the dyeing property of the dye.

Further, the same sample was subjected to a developing treatment in the same manner as in Example 8 to examine the residual color.

The results are shown in Table 9.

Comparative compounds E, F, G and H are as follows.

As is clear from the results of Table 9, Samples 17 to 2 of the present invention
It can be seen that No. 7 has almost no residual color in the development process and has excellent dyeability to gelatin.

Example 11 Exemplified compound 2-7 was dispersed and dissolved in 5 g of water (100 ml), and this was mixed with 250 g of a 14% gelatin solution and stirred using a colloid mill. This composition was coated on a cellulose triacetate film support so that the coating amount was 8 g / m ² , and a sample was set to 100.

Then, instead of the exemplary compound 2-7, the exemplary compound 2-9,
2-10, 2-12, 2-14, 2-18, and 2-20 were used to prepare samples in the same manner.
It was set to 6. Further, using the comparative compounds (A), (B), (C) and (D), samples 107 to 11 were prepared in the same manner as above.
0 was created. Further, when mixing an aqueous solution of the compound of Exemplified Compound 2-7 with a gelatin solution, tricresyl phosphate (dye / oil ratio = 1), ethyl acetate, and p-dodecylbenzenesulfonic acid sodium soda as an emulsifier were added to emulsify. Sample 111 is prepared by applying the dispersed material.
And

Sample 112 was obtained by similarly dispersing and applying polyethyl acrylate (dye / polymer ratio = 1) in place of tricresyl phosphate of sample 111.

Each sample thus obtained was cut into 5 cm ² , and its visible absorption spectrum was measured. The sample is then 38
It was washed with water (20 ml) for 3 minutes at ℃. After the sample was dried, the absorption spectrum was measured again, and the dyeing property of the dye was evaluated according to the following formula.

The decolorizing property was evaluated by immersing the prepared sample (5 cm ² ) in a treatment liquid having the following composition at 38 ° C. for 3 minutes, washing with water and drying, and then measuring absorption spectrum.

Treatment liquid composition H ₂ O 1000 cc Metol 2 g Hydroquinone 5 g Sodium sulfite 70 g Calcium carbonate 40 g Potassium bromide 2 g The results obtained are shown in Table 10.

Comparative compound (A) Comparative compound (B) Comparative compound (C) Comparative compound (D) As is clear from the results shown in Table 10, all of the samples according to the present invention are stable even after washing with water and have sufficient dyeability, and when treated, they are substantially safe decolorizing properties. Indicates.

Further, as can be seen from the results of Samples 111 and 112, even when the dye of the present invention is emulsified and dispersed, excellent dyeing property and decoloring property are similarly exhibited.

Example 12 A multilayer color light-sensitive material sample was prepared by forming each layer on a polyethylene terephthalate film support in exactly the same manner as in Sample 68 of Example 6.

This sample is referred to as sample 120.

Instead of the yellow colloidal silver in the eighth layer of Sample 120, a dispersion prepared by the same method as in Example 8 except that Exemplified Compound 2-7 was used, and the coating amount of Compound 2-7 was 0.2 g / m ^2. The dye prepared in the same manner as the dye 120 except that it was applied so as to be 121 was 121. Using the comparative compound (C) used in Example 11, a sample prepared in the same manner was used.
And Further, a sample excluding the yellow colloidal silver of the eighth layer of the sample 120 was prepared and used as a sample 123.

The obtained samples 120, 121 and 122 were subjected to wedge exposure by a conventional method and the same developing treatment as in Example 6 was performed.

In addition, as in Example 6, the color developer in the processing step was changed to 4-
(N-ethyl-N-β-hydroxyethylamino) -2
-Preparation of a treatment liquid excluding methylaniline sulfate, treatment of Samples 120 to 123, and treatment of Steps 2 to 6 below to evaluate the decolorizing property of the dye.

The difference between each of the yellow densities of Samples 120 to 122 and the yellow density of Sample 123 was defined as ΔD min ^B.

The results obtained are shown in Table 11.

The sample 121 according to the present invention has a ΔD ^B min value of 0, and there is no problem in decolorization of the dye due to the treatment. In addition, the degree of fogging is lower than when yellow colloidal silver is used. Also, the change in sensitivity of the film over time was less than when yellow colloidal silver was used. In Comparative Sample 122, the dyeing property is not sufficient and the dye diffuses to the other layers, which causes significant desensitization.

Example 13 In exactly the same manner as in Example 7, the first to twelfth layers were coated on a cellulose triacetate film support to prepare a color reversal photographic light-sensitive material, Sample 130.

Then, in place of the yellow colloidal silver of the eighth layer of Sample 130, Exemplified Compound 2-12 was used, and a dispersion prepared in the same manner as in Example 8 was coated with Compound 2-12 in an amount of 0.
A sample 131 was prepared in the same manner as the sample 130 except that the amount of coating was 2 g / m ² .

The obtained sample was subjected to wedge exposure with white light in exactly the same manner as in Example 7, and then subjected to nine stages of development treatment from the first development to the stabilization treatment.

The sample 131 according to the present invention had a good decolorizing property due to the treatment, and the stain in the highlight part was similar to that of the sample 130.

Example 14 A silver halide emulsion composed of silver chlorobromide (5 mol% silver bromide average particle size: 0.25 μm) containing 1.1 × 10 ⁻⁵ mol of Rh per 1 mol of silver was prepared.

This emulsion was divided into 8 parts, to each of which 2-hydroxy-4,6-dichloro-1,3,5-triazine sodium as a hardener and potassium polystyrene sulfonate as a thickener were added, and the emulsion was placed on a polyethylene terephthalate film. The amount of silver applied was 4 g / m ² . This 8
As a protective layer on one emulsion layer, a gelatin solution containing a dye shown in Table 12 or not containing a dye having a gelatin content of 1.
It was applied so as to be 0 g / m ² . As a coating aid for this protective layer, sodium p-dodecylbenzenesulfonate,
As the thickener, the same compound as in the emulsion layer was used.

The sample thus obtained was exposed with a P-607 type printer manufactured by Dainippon Screen Co., Ltd. through an optical wedge, and then developed with a developing solution LD-835 manufactured by Fuji Photo Film Co., Ltd.

The results are shown in Table 12.

Comparative compound A Comparative compound B As is clear from the results of the twelfth bag, in Samples 7 and 8, most of the dyes added to the protective layer diffuse into the emulsion layer, and safelight safety can be obtained, but γ significantly decreases. On the other hand, Samples 2 to 6 of the present invention have safelight safety and residual color equal to or higher than those of Samples 7 and 8, and the diffusion of the dye added to the protective layer to the emulsion layer was not observed. Is very low.

Example 15 Silver chlorobromide containing 1.0 × 10 ⁻⁵ mol of Rh per 1 mol of silver (average particle size containing 5 mol% of silver bromide; 0.22 μ)
Was prepared.

This emulsion was divided into 7 parts and used as a hardener and thickener in Example 1.
A compound similar to that of No. 4 was added and coated on a polyethylene terephthalate film so that the amount of silver was 3.8 g / m ² . Gelatin (1 g / m ² ) on this emulsion layer,
Mordant shown below (amount of 0.5g / m ² ) and 13th
Various dyes shown in the table were dissolved in water and then applied as a protective layer. The same compound as in Example 14 was used as the coating aid.

mordant The sample thus obtained was treated in the same manner as in Example 14, and the relative sensitivity, γ, fog after safelight irradiation, and residual color were tested in the same manner as in Example 14.

The results are shown in Table 13.

As is clear from the results in Table 13, by using the dye in combination with the mordant in the present invention, the diffusion of the dye into the emulsion layer is further reduced as compared with the dye alone, and further reduction of γ is further prevented. The safety can be improved.

Example 16 To a 5% aqueous gelatin solution, the dyes shown in Table 14 were added,
Further, the same hardening agent, thickening agent and coating aid as in Example 14 were added and coated on a polyethylene terephthalate film so that gelatin was 3 g / m ² and dye was 0.25 mmol / m ² .

The sample thus obtained was bashed in water at 40 ° C. for 5 minutes to examine the dyeing property of the dye.

Further, the same sample was subjected to development processing in the same manner as in Example 14 to examine the residual color property.

The results are shown in Table 14.

Comparative compounds C to F Comparative compound G As is clear from the results shown in Table 14, Sample 16 of the present invention
It can be seen that Nos. 26 to 26 have almost no residual color in the development process and have excellent dyeing property to gelatin.

Example 17 5 g of Exemplified Compound 3-1 was dispersed and dissolved in 100 ml of water, 250 g of a 14% gelatin solution was mixed with the solution, and the mixture was stirred using a colloid mill. This composition was coated on a cellulose triacetate film support to give a coating amount of 8 g / m ² to prepare Sample 100.

Then, instead of the exemplified compound 3-1, the exemplified compound 3-3,
Samples were prepared in the same manner using 3-4, 3-5, 3-7, 3-15, and 3-21, and samples 101 to 106 were prepared.
And In addition, comparative compounds (H), (I), (J),
Samples 107-110 using (K) as above
It was created. Further, when mixing an aqueous solution of the compound of Exemplified Compound 3-4 of Sample 102 with a gelatin solution, tricresyl phosphate (dye / oil ratio = 1), ethyl acetate, and p-dodecylbenzenesulfonate sodium as an emulsifier were added. A sample 111 was obtained by applying the emulsion-dispersed product.

Sample 112 was obtained by similarly dispersing and applying polyethyl acrylate (dye / polymer ratio = 1) in place of tricresyl phosphate of sample 111.

Each sample thus obtained was cut into 5 cm ² , and its visible absorption spectrum was measured. The sample is then 38
It was washed with water (20 ml) for 3 minutes at ℃. After the sample is dried, the absorption spectrum is measured again. The dyeability of the dye was evaluated according to the following formula.

The decolorizing property was evaluated by immersing the prepared sample (5 cm ² ) in a treatment liquid having the following composition at 38 ° C. for 3 minutes, washing with water and drying, and then measuring absorption spectrum.

Treatment liquid composition H ₂ O 1000 cc Metol 2 g Hydroquinone 5 g Sodium sulfite 70 g Calcium carbonate 40 g Potassium bromide 2 g The results obtained are shown in Table 15.

Comparative compound (H) Comparative compound (I) Comparative compound (J) Comparative compound (K) As is clear from the results shown in Table 15, all the samples according to the present invention are stable even when washed with water and have sufficient dyeability, and when they are treated, they are substantially completely decolorized. Indicates.

Further, as can be seen from the results of Samples 111 and 112, even when the dye of the present invention is emulsified and dispersed, excellent dyeing property and decoloring property are similarly exhibited.

Example 18 A multilayer color light-sensitive material sample was prepared by forming each layer on a polyethylene terephthalate film support in exactly the same manner as in Sample 68 of Example 6.

This sample is referred to as sample 120.

Instead of the yellow colloidal silver of the eighth layer of Sample 120, a dispersion in which Exemplified Compound 3-4 was dispersed in the same manner as in Sample 102 of Example 17 was used, and the coating amount of Exemplified Compound 3-4 was 0.2 g.
Sample 121 was prepared in the same manner as Sample 120 except that the coating was performed so that the coating amount was / m ² . A sample similarly prepared by using the comparative compound (J) shown in Example 17 was designated as 122. Further, a sample excluding the yellow colloidal silver of the eighth layer of the sample 120 was prepared and used as a sample 123.

Wedge exposure was applied to the obtained samples 120, 121 and 122 by a conventional method, and development processing was performed in exactly the same manner as in Example 6.

Further, in the same manner as in Example 6, 4- (N-ethyl-N-β-hydroxyethylamino) was obtained from the color developer in the processing step.
A treatment liquid from which 2-methylaniline sulfate was removed was prepared, treated with Samples 120 to 123, and subjected to the treatments of Steps 2 to 6 below to evaluate the decolorizing property of the dye.

The difference between each of the yellow densities of Samples 120 to 122 and the yellow density of Sample 123 was defined as ΔD min ^B.

The results obtained are shown in Table 16.

The sample 121 according to the present invention has a ΔD ^B min value of 0, and there is no problem in decolorization of the dye due to the treatment. In addition, the degree of fogging is lower than when yellow colloidal silver is used. Also, the change in sensitivity of the film over time was less than when yellow colloidal silver was used. In Comparative Sample 122, the dyeing property is not sufficient and the dye diffuses to the other layers, which causes significant desensitization.

Example 19 A color reversal photographic light-sensitive material, Sample 130, was prepared by coating the first to twelfth layers on a cellulose triacetate film support in exactly the same manner as in Example 7.

Then, in place of the yellow colloidal silver of the eighth layer of Sample 130, Exemplified Compound 3-15 was prepared, and a dispersion prepared in the same manner as in Example 17 was coated with Compound 3-15 at a coating amount of 0.2 g / m 2. A sample 131 was prepared in the same manner as the sample 130 except that it was applied so as to be ² .

The obtained sample was subjected to wedge exposure with white light in exactly the same manner as in Example 7, and then subjected to nine stages of development treatment from the first development to the stabilization treatment.

The sample 131 according to the present invention had a good decolorizing property by the treatment, and the stain in the highlight part was also the same as that of the sample 130.

Front page continuation (72) Keiichi Adachi, 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture, Fuji Photo Film Co., Ltd. (72) Toshiyuki Watanabe, 210, Nakanuma, Minamiashigara City, Kanagawa Prefecture, (72) Inventor, Ishigaki Kunio 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture, Fuji Photo Film Co., Ltd. (56) Reference JP 61-213839 (JP, A) JP 58-83841 (JP, A) JP 59-211042 (JP, JP, A) A) JP 59-206829 (JP, A) JP 59-37303 (JP, B2) JP 3-63060 (JP, B2)

Claims (9)

[Claims] 1. A silver halide photographic light-sensitive material containing at least one compound represented by the following general formulas (I) to (VI). General formula (I) General formula (II) General formula (III) General formula (IV) General formula (V) General formula (VI) (In the formula, X ₁ , X ₂ , X ₃ , and X ₄ may be the same or different, and are a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, a carbonyl group, a substituted amino group, a carbamoyl group, and sulfamoyl. Represents a group or an alkoxycarbonyl group, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and each represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or Represents a substituted aryl group, acyl group or sulfonyl group.
In I) to (VI), R ₁ , R ₂ or R ₃ , R ₄ may form a 5- or 6-membered ring. Z ₁ , Z ₂ , Z ₃ and Z ₄ may be the same or different and represent an electron-withdrawing group. Also Z ₁ and Z ₂ or Z ₃
And Z ₄ may be linked to each other to form a ring. Z ₅ , Z
₆ may be the same or different and represent an atomic group forming a ring, and Z ₇ and Z ₈ may be the same or different and represent an electron withdrawing group. Y ₁ and Y ₂ represent a divalent linking group, Y ₃ and Y ₄ may be the same or different, and represent a divalent linking group having an electron-withdrawing property. L represents an unsubstituted or substituted methine group. m and n are 0
Or 1. ) 2. In the compound represented by formula (I), (II) or (III), Z ₁ , Z ₂ , Z ₃ and Z ₄ may be the same or different and have 2 to 13 carbon atoms. Acyl group, carbamoyl group having 2 to 13 carbon atoms, carboxyl group, unsubstituted or substituted alkoxycarbonyl group having 2 to 10 carbon atoms, unsubstituted or substituted aryloxycarbonyl group, sulfonyl having 1 to 12 carbon atoms Group, an electron-withdrawing group selected from a sulfamoyl group having 1 to 12 carbon atoms and a cyano group, or an electron-withdrawing group Z ₁ thereof.
And Z ₂ or Z ₃ and Z ₄ are linked to each other to form a pyrazolone ring, a pyrazolotriazole ring, a pyrazoloimidazole ring, an oxindole ring, an oxyinmidazopyridine ring, an isoxazolone ring, a barbituric acid ring, di The silver halide photographic light-sensitive material according to claim 1, which is a ring selected from an oxytetrahydropyridine ring and an indandione ring. 3. In the compound represented by the general formula (IV), Z ₅ and Z ₆ may be the same or different, and a pyrazolone ring, a pyrazolotriazole ring, a pyrazoloimidazole ring, an oxindole ring and an oxyimidazopyridine ring. ,
The silver halide photographic light-sensitive material according to claim 1, which is selected from an isoxazolone ring, a barbituric acid ring, a dioxytetrahydropyridine ring, and an indandione ring. 4. In the compound represented by the general formula (V), Z ₇ and Z ₈ may be the same or different and have a carbon number of 2
An acyl group having 13 to 13 carbon atoms, a carbamoyl group having 2 to 13 carbon atoms,
Carboxyl group, unsubstituted or substituted alkoxycarbonyl group having 2 to 10 carbon atoms, unsubstituted or substituted aryloxycarbonyl group, sulfonyl group having 1 to 12 carbon atoms, sulfamoyl group and cyano group having 1 to 12 carbon atoms The silver halide photographic light-sensitive material according to claim 1, which is an electron-withdrawing group selected from the group consisting of: 5. A silver halide photograph according to claim 1, wherein the compounds represented by formulas (I) to (VI) have 2 to 4 sulfo groups or carboxyl groups or salts thereof in the molecule. Photosensitive material. 6. A compound represented by formula (I), (II) or (III), wherein Z ₁ and Z ₂ or Z ₃ and Z ₄ are linked to each other to form a pyrazolone ring. The described silver halide photographic light-sensitive material. 7. A compound represented by formula (I), (II) or (III) wherein Z ₁ and Z ₂ or Z ₃ and Z ₄ are a cyano group and an optionally substituted benzoyl group. The silver halide photographic light-sensitive material according to claim 1, which is a combination. 8. A silver halide photographic light-sensitive material according to claim 1, which is formed by coating the compounds represented by formulas (I) to (IV) in an amount of 0.001 to 1 g / m ^2. 9. A silver halide photographic light-sensitive material containing a compound represented by the following general formula (I) or (II) having 2 to 4 sulfo groups or salts thereof, is developed. A photographic processing method comprising processing with a developing solution containing sulfite. General formula (I) General formula (II) (In the formula, X ₁ , X ₂ , X ₃ and X ₄ may be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, a carboxy group, a substituted amino group, a carbamoyl group or a sulfamoyl group. R ₁ and R ₂ may be the same or different and each represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, an acyl group. Z ₁ , Z ₂ , Z ₃ , and Z ₄ may be the same or different, and are an acyl group having 2 to 13 carbon atoms, a carbamoyl group having 2 to 13 carbon atoms, a carboxyl group, or carbon. An unsubstituted or substituted alkoxycarbonyl group having a number of 2 to 10, an unsubstituted or substituted aryloxycarbonyl group, and a carbon number of 1
Represents an electron-withdrawing group selected from a sulfonyl group having 12 to 12 carbon atoms, a sulfamoyl group having 1 to 12 carbon atoms and a cyano group. Alternatively, these electron-withdrawing groups Z ₁ and Z ₂ or Z
₃ and Z ₄ are linked to each other to form a pyrazolone ring, a pyrazolotriazole ring, a pyrazoloimidazole ring, an oxindole ring, an oxyimidazopyridine ring, an isoxazolone ring,
It may form a ring selected from a barbituric acid ring, a dioxytetrahydropyridine ring and an indandione ring. Y ₁ and Y ₂ represent a divalent linking group. L represents an unsubstituted or substituted methine group. m and n are 0
Or 1. )